End group effect on the thermo‐sensitive properties of well‐defined water‐soluble polystyrenics with short pendant oligo(ethylene glycol) groups synthesized by nitroxide‐mediated radical polymerization

The effects of hydrophobic chain end groups on the cloud points of thermo‐sensitive water‐soluble polystyrenics were investigated. Well‐defined poly (4‐vinylbenzyl methoxytris(oxyethylene) ether) (PTEGSt) and poly(α‐hydro‐ω‐(4‐vinylbenzyl)tetrakis(oxyethylene)) (PHTrEGSt) were prepared by nitroxide‐mediated radical polymerization using α‐hydrido alkoxyamine initiators including two monomer‐based initiators. The polymers were reduced with (n‐Bu)₃SnH to replace the alkoxyamine end group with hydrogen. In the studied molecular weight range (M_n,GPC = 3000 to 28,000 g/mol), we found that the hydrophobic end groups decreased the cloud point by 1–20 °C depending on the molecular weight and the largest depression was observed at the lowest molar mass. The cloud points of PTEGSt and PHTrEGSt with two hydrophobic end groups, phenylethyl and alkoxyamine, exhibited a monotonic increase with the increase of molecular weight. For polymers with only one hydrophobic end group, either phenylethyl or alkoxyamine, the cloud point initially increased with the increase of molecular weight but leveled off/decreased slightly with further increasing molar mass. For polymers with essentially no end groups, the cloud point decreased with the increase of chain length, which represents the “true” molecular weight dependence of the cloud point. The observed molecular weight dependences of the cloud points of polystyrenics with hydrophobic end group(s) are believed to result from the combined end group effect and “true” molecular weight effect. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3707–3721, 2007     

Bioactive mesoglobules of poly(di(ethylene glycol) monomethyl ether methacrylate)–peptide conjugate

This study describes the synthesis and aggregation behavior of thermosensitive poly(di(ethylene glycol) monomethyl ether methacrylate) (P(DEGMA‐ME)) conjugated with the fluorescently labeled pentapeptide glycine‐arginine‐lysine‐phenylalanine‐glycine‐dansyl (GRKFG‐Dns). The GRKFG‐Dns was obtained using Fmoc solid‐phase peptide synthesis and was modified with 2‐bromopropionic acid to initiate an atom transfer radical polymerization of di(ethylene glycol) monomethyl ether methacrylate (DEGMA‐ME). The polymerization led to a well‐defined P(DEGMA‐ME)–GRKFG‐Dns conjugate with a number average molar mass of 108,000 g/mol. The pentapeptide acted as a hydrophilic moiety that increased the phase transition temperature compared to the P(DEGMA‐ME) homopolymer of similar molar mass. The bioconjugate macromolecules aggregated in dilute aqueous solution into spherical particles (mesoglobules). The sizes of aggregates were easily controlled by changing the concentration and heating rate of the P(DEGMA‐ME)‐GRKFG‐Dns solution. The weight average molar masses and sizes of mesoglobules were determined based on light scattering measurements. Enzymatic hydrolysis of the bioconjugate in dilute solution was performed at temperatures below and above the cloud point temperature of the bioconjugate. The peptides were fully accessible to enzymatic digestion even when the macromolecules were aggregated to mesoglobules, indicating that the peptide segments in mesoglobules formed the external shell of the nanoparticles and could be easily released by enzymes. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Temperature‐sensitive hyperbranched poly(glycidol)s with oligo(ethylene glycol) monoethers

Temperature‐dependent polymers are intelligent materials. In this study, biocompatible and temperature‐dependent hyperbranched poly(glycidol)s (HPGs) were synthesized and characterized. HPGs were succinylated then modified with the oligo(ethylene glycol) monoethers (OEG) for example methoxy di(ethylene glycol), methoxy tri(ethylene glycol), methoxy tetra(ethylene glycol), ethoxy di(ethylene glycol), ethoxy tri(ethylene glycol), and methoxy poly(ethylene glycol)s at different ratios. These polymers exhibited phase transitions at a specific temperature (the cloud point), depending on the composition of OEG. By tuning the composition of OEG in the polymer, thermosensitive polymers with cloud point near body temperature were produced. Endothermic peaks of these polymers were observed in the vicinity of the cloud point. It is suggested that at temperatures below the cloud point the polymers formed hydrophobic shells and became more hydrophobic at temperatures above the cloud point. Because they exhibited no cytotoxicity, these temperature‐sensitive polymers are useful for biomedical applications. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4047–4054, 2010     

Quadruple click reactions for the synthesis of cysteine‐terminated linear multiblock copolymers

Synthesis of cysteine‐terminated linear polystyrene (PS)‐b‐poly(ε‐caprolactone) (PCL)‐b‐poly(methyl methacrylate) (PMMA)/or poly(tert‐butyl acrylate)(PtBA)‐b‐poly(ethylene glycol) (PEG) copolymers was carried out using sequential quadruple click reactions including thiol‐ene, copper‐catalyzed azide–alkyne cycloaddition (CuAAC), Diels–Alder, and nitroxide radical coupling (NRC) reactions. N‐acetyl‐L ‐cysteine methyl ester was first clicked with α‐allyl‐ω‐azide‐terminated PS via thiol‐ene reaction to create α‐cysteine‐ω‐azide‐terminated PS. Subsequent CuAAC reaction with PCL, followed by the introduction of the PMMA/or PtBA and PEG blocks via Diels–Alder and NRC, respectively, yielded final cysteine‐terminated multiblock copolymers. By ¹H NMR spectroscopy, the DP_ns of the blocks in the final multiblock copolymers were found to be close to those of the related polymer precursors, indicating that highly efficient click reactions occurred for polymer–polymer coupling. Successful quadruple click reactions were also confirmed by gel permeation chromatography. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis and properties of comb polymers with semirigid mesogen‐jacketed polymers as side chains

A series of novel comb polymers, poly{2,5‐bis[(4‐methoxyphenyl)oxycarbonyl]styrene}‐g‐polystyrene (PMPCS‐g‐PS), with mesogen‐jacketed rigid side chains were synthesized by the “grafting onto” method from α‐yne‐terminated PMPCS (side chain) and poly(vinylbenzyl azide) (backbone) by Cu(I)‐catalyzed 1,3‐dipolar cycloaddition click reaction. The α‐yne‐terminated PMPCS was synthesized by Cu(I)‐catalyzed atom transfer radical polymerization initiated by a yne‐functional initiator. Poly(vinylbenzyl azide) was prepared by polymerizing vinylbenzyl chloride using nitroxide mediated radical polymerization to obtain poly(vinylbenzyl chloride) as the precursor which was then converted to the azide derivative. The chemical structure and architectures of PMPCS comb polymers were confirmed by ¹H NMR, gel permeation chromatography, and multiangle laser light scattering. Both surface morphologies and solution behaviors were investigated. Surface morphologies of PMPCS combs on different surfaces were investigated by scanning probe microscopy. PMPCS combs showed different aggregation morphologies when depositing on silicon wafers with/without chemical modification. The PMPCS comb polymers transferred to polymer‐modified silicon wafers using the Langmuir‐Blodgett technique showed a worm‐like chain conformation. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Sol–gel transition behavior of biodegradable three‐arm and four‐arm star‐shaped PLGA–PEG block copolymer aqueous solution

Two types of temperature‐sensitive biodegradable three‐arm and four‐arm star‐shaped poly(DL ‐lactic acid‐co‐glycolic acid‐b‐ethylene glycol) (3‐arm and 4‐arm PLGA–PEG) were successfully synthesized via the coupling reaction of 3‐arm and 4‐arm PLGA and α‐monocarboxyl‐ω‐monomethoxypoly(ethylene glycol) (CMPEG). In dilute aqueous solutions, star PLGA–PEGs showed the temperature‐ and concentration‐dependent formation and aggregation of micelles over specific concentration and specific temperature. With increasing the molecular weight and the relative hydrophobicity of hydrophobic PLGA block, critical micelle temperature (CMT) decreased. Aqueous solution of 4‐arm PLGA–PEG started to form micelles at lower temperature and showed sharper temperature‐dependent growth in micelle size. These results are due to the enhanced hydrophobicity of PLGA block. On the other hand, at high concentration, two types of 3‐arm and 4‐arm PLGA–PEG showed sol–gel–sol transition behavior as the temperature was increased. The 3‐arm and 4‐arm PLGA–PEG showed sol–gel transition at higher polymer concentrations (above 24 wt %) than the PEG–PLGA–PEG triblock copolymer. As the molecular weight and the relative hydrophobicity of PLGA block increased, the critical gel concentration (CGC) decreased. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 888–899, 2006     

Free radical and nitroxide mediated polymerization of hydroxy–functional acrylates prepared via lipase–catalyzed transacylation reactions

3‐Hydroxypropyl acrylate, 4‐hydroxybutyl acrylate, 2‐methyl‐3‐hydroxypropyl acrylate, 2‐hydroxypropyl acrylate, neopentyl glycol acrylate, glyceryl acrylate, and dihydroxyhexyl acrylate were prepared via transacylation reaction of methyl acrylate with diols and triols catalyzed by Candida antarctica lipase B. After removal of the enzyme by filtration and the methyl acrylate by distillation, the monomers were polymerized via free radical polymerization (FRP) with azobisisobutyronitrile as initiator and nitroxide mediated polymerization (NMP) employing Blocbuilder? alkoxyamine initiator and SG‐1 free nitroxide resulting in hydroxy functional poly(acrylates). The NMP kinetics are discussed in detail. In addition, the polymers obtained by FRP and NMP are compared and the results are related to the amount of bisacrylates that are present in the initial monomer mixtures resulting from the transacylation reactions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2610–2621, 2010     

ABC‐type hetero‐arm star terpolymers through “Click” chemistry

Hetero‐arm star ABC‐type terpolymers, poly(methyl methacrylate)‐polystyrene‐poly(tert‐butyl acrylate) (PMMA‐PS‐PtBA) and PMMA‐PS‐poly(ethylene glycol) (PEG), were prepared by using “Click” chemistry strategy. For this, first, PMMA‐b‐PS with alkyne functional group at the junction point was obtained from successive atom transfer radical polymerization (ATRP) and nitroxide‐mediated radical polymerization (NMP) routes. Furthermore, PtBA obtained from ATRP of tBA and commercially available monohydroxyl PEG were efficiently converted to the azide end‐functionalized polymers. As a second step, the alkyne and azide functional polymers were reacted to give the hetero‐arm star polymers in the presence of CuBr/N,N,N′,N″,N″‐pentamethyldiethylenetriamine ( PMDETA) in DMF at room temperature for 24 h. The hetero‐arm star polymers were characterized by ¹H NMR, GPC, and DSC. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5699–5707, 2006     

Controlled synthesis of thermoresponsive polymers derived from l‐Lysine,a biorenewable resource

Renewable lysine was cyclized to its corresponding α‐amino‐ε‐caprolactam and then underwent the reaction with acryloyl chloride to harvest a 2‐acrylamido‐caprolactam (ACL) monomer. Subsequent reversible addition–fragmentation chain transfer copolymerization of the obtained monomer with oligo(ethylene glycol)acrylate (OEGA) gave well‐defined P(ACL‐co‐OEGA) with low distribution. Nuclear magnetic resonance , size exclusion chromatography, and matrix‐assisted laser desorption ionization–time‐of‐flight–mass spectrometry measurements indicated the controlled feature of the polymerization. Moreover, the resultant copolymers demonstrated thermoresponsiveness, and the cloud points (T_cp) can be adjusted from 34 to 79 °C, by changing pH values, and the fraction of cyclic lysine. These results suggested that these lysine‐based thermoresponsive polymers might be used as new materials in biomedical fields. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 862–868     

Heteroarm H‐shaped terpolymers through click reaction

Heteroarm H‐shaped terpolymers, (polystyrene)(poly(methyl methacrylate))‐ poly(tert‐butyl acrylate)‐(polystyrene)(poly(methyl methacrylate)), (PS)(PMMA)‐PtBA‐(PMMA)(PS), and, (PS)(PMMA)‐poly(ethylene glycol)(PEG)‐(PMMA)(PS), through click reaction strategy between PS‐PMMA copolymer (as side chains) with an alkyne functional group at the junction point and diazide end‐functionalized PtBA or PEG (as a main chain). PS‐PMMA with alkyne functional group was prepared by sequential living radical polymerizations such as the nitroxide mediated (NMP) and the metal mediated‐living radical polymerization (ATRP) routes. The obtained H‐shaped polymers were characterized by using ¹H‐NMR, GPC, DSC, and AFM measurements. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1055–1065, 2007     

Effects of polydepsipeptide side‐chain groups on the temperature sensitivity of triblock copolymers composed of polydepsipeptides and poly(ethylene glycol)

To develop new types of biodegradable polymers possessing predictable responses to changes in temperature, ABA‐type and BAB‐type triblock copolymers composed of various polydepsipeptides (PDP) and poly(ethylene glycol) (PEG) (PDP‐PEG‐PDP and PEG‐PDP‐PEG) were synthesized. The specific focus of this study was on the effect of the different side‐chain groups of various amino acids on the temperature‐responsive behavior of the triblock copolymers. An ABA‐type triblock copolymer containing the less hydrophobic glycine (PGG‐PEG‐PGG) did not exhibit any temperature‐responsive behavior; however, ABA‐type triblock copolymers containing the hydrophobic α‐amino acids, L ‐leucine and L ‐phenylalanine (PGL‐PEG‐PGL or PGF‐PEG‐PGF), did exhibit temperature‐responsive behavior. The cloud point of PGF‐PEG‐PGF was 10 °C lower than that of PGL‐PEG‐PGL. It can be possible to control temperature‐sensitivity by changing not only PDP segment length but also kind of α‐amino acid in PDP segment. Moreover, BAB‐type triblock copolymer containing L ‐leucine (PEG‐PGL‐PEG) showed temperature‐responsive sol‐gel transition. Because polydepsipeptides are biodegradable polymers, the information obtained in this study is useful to design biodegradable injectable polymers having controllable temperature‐sensitivity for biomedical use.© 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 3892–3903, 2009     

Novel AB crosslinked polymer networks from telechelic 4‐vinylbenzyl carbamate terminated polyurethanes and different vinyl monomers

Novel AB crosslinked polymer (ABCP) networks were synthesized from telechelic 4‐vinylbenzyl carbamate terminated polyurethanes and monomers such as styrene, 4‐vinylpyridine, methyl methacrylate and butyl acrylate. Telechelic 4‐vinylbenzyl carbamate terminated polyurethanes were synthesized from polypropylene glycol‐based NCO‐terminated polyurethane and vinylbenzyl alcohol. Effect of changing the molecular weight of polypropylene glycol on the static and dynamic mechanical properties of ABCP networks from polyurethane‐polymethyl methacrylate was studied in detail. Dynamic mechanical thermal analysis results show that polymethyl methacrylate and polystyrene‐based ABCPs have good damping over a broad temperature range. ABCP networks prepared from 4‐vinylbenzyl carbamate terminated polyurethane and different monomers such as methyl methacrylate, butyl acrylate and styrene exhibit single tan δ_max value which implies excellent interlocking between the two polymers present in the ABCP networks. Static mechanical studies showed that methyl methacrylate and styrene‐based ABCP networks exhibit better tensile properties compared to other ABCP networks from butyl acrylate and 4‐vinyl pyridine monomers. Thermogravimetric analysis results revealed that the ABCP networks showed an improved thermal stability. Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis,Characterization, and thermoresponsive properties of Helical Polypeptides Derivatized from Poly(γ−4‐(3‐chloropropoxycarbonyl)benzyl‐L‐glutamate)

A series of side‐chain‐functionalized α‐helical polypeptides, i.e., poly(γ‐4‐(3‐chloropropoxycarbonyl)benzyl‐_L‐glutamate) (6) have been prepared from n‐butylamine initiated ring‐opening polymerization (ROP) of γ‐4‐(3‐chloropropoxycarbonyl)benzyl‐_L‐glutamic acid‐based N‐carboxyanhydride. Polypeptides bearing oligo‐ethylene‐glycol (OEG) groups or 1‐butylimidazolium salts were prepared from 6 via copper‐mediated [2+3] alkyne‐azide 1,3‐dipolar cycloaddition or nuleophilic substitution, respectively. CD and FTIR analysis revealed that the polymers adopt α‐helical conformations both in solution and the solid state. Polymers bearing OEG (m = 3) side‐chains showed reversible LCST‐type phase transition behaviors in water while polymers bearing 1‐butylimidazolium and I^? counter‐anions exhibited reversible UCST‐type transitions in water. Variable‐temperature UV‐vis analysis revealed that the phase transition temperatures (T_pts) were dependent on the main‐chain length and polymeric concentration. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2469–2480     

Synthesis of end‐functionalized AB copolymers. II. Synthesis and characterization of carboxyl‐terminated poly(ethylene glycol)–poly(amino acid) block copolymers

AB block copolymers composed of hydrophilic poly(ethylene glycol) (PEG) and hydrophobic poly(amino acid) with a carboxyl group at the end of PEG were synthesized with α‐carboxylic sodium‐ω‐amino‐PEG as a macroinitiator for the ring‐opening polymerization of N‐carboxy anhydride. Characterizations by ¹H NMR, IR, and gel permeation chromatography were carried out to confirm that the diblock copolymers were formed. In aqueous media this copolymer formed self‐associated polymer micelles that have a carboxyl group on the surface. The carboxyl groups located at the outer shell of the polymeric micelle were expected to combine with ligands to target specific cell populations. The diameter of the polymer micelles was in the range of 30–80 nm. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3527–3536, 2004     

Stimulus‐responsive polymers based on 2‐hydroxypropyl acrylate prepared by RAFT polymerization

Homopolymerization and diblock copolymerization of 2‐hydroxypropyl acrylate (HPA) has been conducted using reversible addition fragmentation chain transfer (RAFT) chemistry in tert‐butanol at 80 °C. PHPA homopolymers were obtained with high conversions and narrow molecular weight distributions over a wide range of target degrees of polymerization. Like its poly(2‐hydroxyethyl methacrylate) isomer, PHPA homopolymer exhibits inverse temperature solubility in dilute aqueous solution, with cloud points increasing systematically on lowering the mean chain length. The nature of the end groups is shown to significantly affect the cloud point, whereas no effect of concentration was observed over the PHPA concentration range investigated. Various thermoresponsive PHPA‐based diblock copolymers were prepared via one‐pot syntheses in which the second block was either permanently hydrophilic or pH‐responsive. Preliminary studies confirmed that poly(ethylene oxide)‐poly(2‐hydroxypropyl acrylate) (PEO₄₅‐PHPA₄₈) and poly(2‐hydroxypropyl acrylate)‐ poly(2‐hydroxyethyl acrylate) (PHPA₄₉‐PHEA₆₈)diblock copolymers formed well‐defined PHPA‐core micelles in 10 mM sodium nitrate solution at 40 °C and 70 °C with mean hydrodynamic diameters of 20 nm and 35 nm, respectively. In contrast, most other PHPA‐based diblock copolymers investigated formed larger colloidal aggregates in 10 mM NaNO₃ solution at elevated temperatures. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2032–2043, 2010     

Degradable alternating polyperoxides from poly(ethylene glycol)‐substituted styrenic monomers with water solubility and thermoresponsiveness

Water soluble alternating copolymers were prepared by oxidative free radical copolymerization of 4‐vinylbenzyl methoxypoly(oxyethylene) ether (PEGSt) and molecular oxygen at 50 °C. NMR spectroscopy established alternate sequence of PEGSt and peroxy bonds ( O O ) along the polymer main‐chain. The obtained polymers show temperature induced hydrophilic to hydrophobic phase separation, confirmed by UV‐visible spectroscopy and dynamic light scattering. The cloud point temperature (T_CP) of the polymers can be tuned by changing the chain length of side‐chain poly(ethylene oxide) and incorporation of hydrophobic methyl methacrylate in the copolyperoxides. Exothermic degradation of these polyperoxides was confirmed by differential scanning calorimetry and the degradation products have been characterized by electron impact mass spectroscopy. Finally, N,N‐dimethylacrylamide was polymerized in the presence of these polyperoxides in toluene, highlighting their potential as polymeric free radical initiator during polymerization of vinyl monomers. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2030–2038     

Unusual effect of molecular weight and concentration on thermoresponsive behaviors of well‐defined water‐soluble semirigid polymers

A series of water‐soluble semirigid thermoresponsive polymers with well‐defined molecular weights based on mesogen‐jacketed liquid crystal polymers (MJLCPs), poly[bis(N‐hydroxyisopropyl pyrrolidone) 2‐vinylterephthalate] (PHIPPVTA) have been synthesized via reversible addition fragmentation chain transfer (RAFT) polymerization. Dynamic light scattering (DLS) revealed that the novel monomer and polymers have thermoresponsive properties with cloud point in the range between 10 and 90 °C. The cloud point was increased by 56.2 °C when the polymer molecular weight increased from 0.47 × 10⁴ g mol^?1 to 3.69 × 10⁴ g mol^?1. In addition, the cloud point of PHIPPVTA was decreased by 18.8 °C with the increase of polymer concentration from 5 to 10 mg mL^?1. A slight increase (0.1–3.5 °C) of cloud point has been observed after knocking off the end‐groups of PHIPPVTA. Moreover, the cloud point of polymer increased with increasing of its molecular weight with or without the trithiocarbonate end‐groups, which showed the opposite trend comparing with other thermoresponsive polymers with flexible backbones. These polymers show a dramatic solvent isotopic effect that the cloud point in D₂O was lower than in H₂O. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Synthesis of star polymers via nitroxide mediated free‐radical polymerization: A “core‐first” approach using resorcinarene‐based alkoxyamine initiators

The synthesis of new octafunctional alkoxyamine initiators for nitroxide‐mediated radical polymerization (NMRP), by the derivatization of resorcinarene with nitroxide free radicals viz TEMPO and a freshly prepared phosphonylated nitroxide, is described. The efficiency of these initiators toward the controlled radical polymerization of styrene and tert‐butyl acrylate is investigated in detail. Linear analogues of these multifunctional initiators were also prepared to compare and evaluate their initiation efficiency. The favorable conditions for polymerization were optimized by varying the concentration of initiators and free nitroxides, reaction conditions, etc., to obtain well‐defined star polymers. Star polystyrene thus obtained were further used as macro‐initiator for the block copolymerization with tert‐butyl acrylate. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 5559–5572, 2007     

Steric hindrance effect on thermo‐responsive behaviors of well‐defined water‐soluble semi‐rigid polymers

Three series of water‐soluble semi‐rigid thermo‐responsive polymers with well‐defined molecular weights based on mesogen‐jacketed liquid crystal polymers, poly[bis(N‐(2‐hydroxypropyl) pyrrolidone) 2‐vinylterephthalate] [P(2‐HPPVTA)], poly[bis(N‐(1‐methyl‐2‐hydroxyethyl) pyrrolidone) 2‐vinylterephthalate] [P(1‐M‐2‐HEPVTA)] and poly[bis(N‐hydroxypropyl pyrrolidone) 2‐vinylterephthalate] (PHPPVTA) have been synthesized via reversible addition‐fragmentation chain transfer polymerization. The steric hindrance effects on liquid crystalline property and thermo‐responsive behaviors of semi‐rigid water‐soluble polymers (P(2‐HPPVTA), P(1‐M‐2‐HEPVTA), and PHPPVTA) were carefully investigated. From molecular structure, the steric hindrance of P(1‐M‐2‐HEPVTA) is stronger than that of P(2‐HPPVTA). Polarized light microscope and one‐dimensional wide‐angle X‐ray diffraction revealed that both the P(2‐HPPVTA) and P(1‐M‐2‐HEPVTA) display a columnar nematic phase, indicating that the steric hindrance effect do not affect liquid crystalline behavior of the polymers. The dynamic light scattering results demonstrated that P(1‐M‐2‐HEPVTA) exhibited lower cloud point compared with that of P(2‐HPPVTA) at the same mass concentration and the same molecular weight. The more significant molecular weight and concentration dependence on cloud point have been observed in P(2‐HPPVTA) solution than in P(1‐M‐2‐HEPVTA) solution. We also discovered that the cloud points of both P(2‐HPPVTA) and P(1‐M‐2‐HEPVTA) solution are lower in D₂O than in H₂O. It is noted that the cloud point of PM‐2 is 9.9 °C lower in D₂O than in H₂O, much less pronounced than the cloud point difference of PH‐2. The differences of thermo‐responsive behaviors between P(2‐HPPVTA) and P(1‐M‐2‐HEPVTA) were resulted from the steric hindrance effect existed in their side groups. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3429–3438     

A library of thermoresponsive PEG-based methacrylate homopolymers: How do the molar mass and number of ethylene glycol groups affect the cloud point?

In this study, a novel library of thermoresponsive homopolymers based on poly (ethylene glycol) (EG) (m)ethyl ether methacrylate monomers is presented. Twenty-seven EG based homopolymers were synthesized and three parameters, the molar mass (MM), the number of the ethylene glycol groups in the monomer, and the chemistry of the functional side group were varied to investigate how these affect their thermoresponsive behavior. The targeted MMs of these polymers are varied from 2560, 5000, 8200 to 12,000 g mol⁻¹. Seven PEG-based monomers were investigated: ethylene glycol methyl ether methacrylate (MEGMA), ethylene glycol ethyl ether methacrylate (EEGMA), di(ethylene glycol) methyl ether methacrylate (DEGMA), tri(ethylene glycol) methyl ether methacrylate (TEGMA), tri(ethylene glycol) ethyl ether methacrylate (TEGEMA), penta(ethylene glycol) methyl ether methacrylate (PEGMA), nona(ethylene glycol) methyl ether methacrylate (NEGMA). Homopolymers of 2-(dimethylamino) ethyl methacrylate (DMAEMA) were also synthesized for comparison. The cloud points of these homopolymers were tested in different solvents and it was observed that it decreases as the number of EG group was decreased or the MM increased. Interestingly, the end functional group (methoxy or ethoxy) of the side group has an effect as well and is even more dominant than the number of EG groups.